Substituted tertiary phosphine oxides



United States atent dice 3,117,165 SUBSTETUTED TERTIARY PHOSPHINE OXIDES Martin Epstein, Stamford, Conn, assignor to American Cyanamid Company, Stamford, Conn, a corporation of Maine No Drawing. Filed Apr. 26, 1962, Ser. No. 190,266 5 Claims. (Cl. 260-6065) The present invention relates to tertiary alpha-alkoxyphosplhine oxides of the formula R2i JR' wherein R represents halo-substituted or unsubstituted alkyl (C -C halo-substituted or unsubstiuted cyclo alkyl, and halo-substituted or unsubstituted aryl; R represents halo-substitut'ed or unsubstituted aryl and R" represents lower alkyl.

The novel products of the present invention are prepared by reacting a hydroxy-substituted tertiary phosphine of the formula with a lower alkyl alcohol of the formula ROH and a peroxide of the formula XOOY. R, R and R in the reactant formulae just given have the same meaning given above for the product formula; X represents hydrogen, alkyl, or acyl; and Y represents hydrogen, alkyl or ac X and Y may represent identical moieties or different moieties. The following is a typical embodiment:

A o crn The tertiary phosphine reactants contemplated herein are prepared in a conventional manner by bringing to gether a secondary p hosphine and an aromatic aldehyde, such as benzaldehyde. In order to prepare the tertiary phcsphine reactant of the typical embodiment just given diphenylphosp-hine is brought into intimate contact with benz aldehyde under mildy acidic conditions, such as in the presence of a dilute mineral acid.

In the absence of a lower alkyl alcohol, treatment of the alpha-hydroxyplhosphine reactants contemplated herein with peroxide oxidizing agents of the type defined above yields the corresponding tertiary phosphine oxides in lieu of the tertiary alpha alkoxyphosphine oxides of the present invention. The following example illustrates this clearly:

The reason the alpha-alkoxyphosphine oxide of the present invention results instead of alpha-hydroxy-phosplhine oxide is not understood. The surprising results of the present invention, however, provide a whole new class of compounds in a simple and straight-forward manner.

Typical hydroxy-substituted tertiary phospliine reactants within the purview of the instant discovery are the unsubstituted and \halo substituted phosphines which follow: dimethyl alpha hydroxybenzylphcsplhine, dipentyl alpha hydroxybenzylphosphine, didodecyl-alphahydroxy-1maphtliyl-metihyhphosphine, dioctadecyl-alphahydroxybenzylphosphine, dicycloh-exyl alpha-hydroxy-lnaphthylmethvlphosphine, dicyclopentyl alpha-hydroxybenzylphosphine, diphenyl alpha hydroxybenzylphosphine, dinaphthyl alpha hydroxybenzylphosphine, bis- (parabromophenyl) -alpha-hydroxybenzylphosphine, bis- (Z-chlorob utyl -alpha-hvdroxybenzylphosphine, diphcnylalpha hydroxy 7 bro-mo-lnaphthylmethylp henylplhosa phine, bis(meta-chlorocyclohexvl) alpha-hydroxybenzylphosphine, ethylcyclohexyl 'alpha-hydrobenzylphosphine, and the like. It follows fromthis list that representative inert substituents contemplated for moieties R and R are h alo-substituents, such as bromo-, chloro-, and the like.

While hydrogen peroxide and organic peroxides of the formula XOOY, defined above, are preferred reactants within the concept of the instant invention, almost any organic peroxide or organic hydrope roxide may be employed. The following are merely typical: hydrogen peroxide, tertiary-butvl-hydroperox-ide, ditertiary butyl peroxide, benzoyl peroxide, lauroyl peroxide, di-acetyl peroxide, tertiary-butyl perbenzoate.

The alcohol reactants of the present invention are preferably used in excess of the stoiohiometric quantity required for reaction. Thus, the lower alkanol serves as a reactant and a solvent. 1

The hydroxy-substituted phosphine reactant, the peroxide reactant =and the lower alkanol reactant need only be present in a 1:1:1 ratio, and any practical excess of the alk-anol relative to the remaining reactants may be employed satisfactorily. If desired, the peroxide may be present in excess of the hydroxy-subs-tituted tertiary phosphine, and vice versa: It follows from this, therefore, that the ratio in which the reactants are present is not critical, as further evidenced from Table l, infra.

Generally the reaction products are recrystallized in an inert solvent, such as aoetonitrile, lower alkanol, or the like, for best results. This is not absolutely necessary, however.

While best results are achieved at reflux temperatures of the lower alkancl solvent, a wide range of temperatures may be employed. For example, temperatures in the range of 0 C. to C. are suitable.

The products of the present invention are useful as gasoline additives. For example, up to about 10 grams of any one of the tertiary alpha-alkoxyphosphine oxides of the present invention, when dissolved in one gallon of gasoline, aifords protection against misfiring, surface ignition and the like. In addition, the novel compounds of the present invention are particularly useful as sequestering agents in the selective removal of heavy metal values from mixtures containing ions, such as nickel, cobalt, copper, iron and uranyl in the presence of alkali and alkaline earth ions. For instance, uranyl values can be selectively leached from an ore containing the same by employing techniques known in the art, as shown by Blake et al. in the Atomic Energy Commission Report ORNL-1903, May 13, 1955.

The present invention will best be understood from the following examples which are deemed illustrative and not limiting, unless, of course, limitations contained therein appear in the appended claims:

EXAMPLE I Diphenyl-Alpha-Meth0xybenzylphosphine Oxide A solution of 15.7 grams of diphenylphosphine (0.084

4 EXAMPLE 1v Diphenyl-Alplza-Ethoxybenzylphosphine Oxide Example !I is repeated in every essential respect with the exception that ethanol is used in lieu of methanol and the corresponding product, diphenyl-alpha-ethoxybenzylphosphine oxide, is recovered.

TABLE I 9 Example Temp Ratio,

No. OH 11:13 O i) ()R RzP-CI'IR' IVOH XOOY Rz1-CIIR V (1imethyl-alpha-liydroxybenmethanoL. hydrogen peroxide.. 65 1:10zl diniethyl-alpha-methoxyzylphosphine. benzylphosphine oxide.

VI dipentyl-alpha-hydroxybenpropanoL- tertiary-butyl-hy- 98 1:7 :1 dipentyl-ulpha-propoxyzylphosphine. (Ire-peroxide. benzylphesphine oxide.

VII didodecyl-alpha-hydroxynaphbutanol..- ditertiary-butyl- 110 1:5:2 didodecyl-alpha-bntoxythylmethylphosphine. peroxide. naphthylmetliylphosphine oxide.

VIII dioetadeeyl-alpha-hydroxyethanoL... benzoyl peroxide. 80 1:10:1 dioetedeeyl-alpha-ethoxyhenzylphosphine. benzylpltosphine oxide.

IX dieycloliexyl-alpha-hydroxymethanoL. lauroyl peroxide..." 65 2:5:1 dicyclehexyl-slpha-menaphthylmethylphosplline. thoxynaphtllylniethylpliosphine oxide.

X dieyelopentyl-nlpha-hydroxydo dl-acetyl peroxide. 50 1:15z1 dicyclopentyl-nlpha-mebenzylphosphine. tlloxybenzylphosplliue exit e.

XI diphenyl-alpha-hydroxybenethanoL... tertlary-butyl-per- 1:10:1 diphe1iylelpha-ethoxyzylphosphine. beuzoate. benzylphesphine oxide.

XII dinaphthyl-alpha-liydroxybenbutanol..- hydrogen peroxide- 1:12z2 dinephthyl-olplia-butexyzylphosphine. henzylphosphine oxide.

XIII bis(para-bromophenyl)-a1phaet11anol. do 90 1;20:1 bis(para-bromophenyD- hydroxybenzyl-phcsphine. alpha-etlioxybenzylphosphine oxide.

XIV bis(Z-elilorobutyl)-a1pha'hypropanoL- benzoyl peroxide. 10 1:911 bis(2-chlorobutyl)-a1pha.-

droxybenzylphosphine. propexyuenzylphosphine oxide.

XV bis(3-brom0nonyD-alpha-hybutanol.. di-aeetyl peroxide... 85 1:10:1 bis(3-bromononyD-alphadroxybenzylphosphine. bugxybenzylpliosphine OX1 e.

XVI diphenyl-alpha-hydroxy-7- ethan0l... tertiary butylhy- 80 1:512 diphenyl-alpha ethoxy-7- brornonaphthylmethylphesdro-peroxide. bromo-l-naphthylphine. methylphosphine oxide.

XVII bis(mete-ehloroeyelohexyD-almothanoL. lauroyl peroxide..... 75 1:7:1 bis(rneta-ehloroeyelopl1a-hydroxy-benzylphoshexyD-alpha-methoxyphine. benzylphosphine oxide.

XVIII.... etliyleyelohexyl-alpha-hydroxyethan0l.. benzoyl peroxide.-.. 4O 119:1 ethylcyolohexyl-alphapara-ehloro-benzylphospine. ethnxy-para-ehlore-benzylpliospliine oxide.

rate to reflux the resulting solution. The solvent is evaporated and the remaining residue triturated with ether to yield 23.6 grams of diphenyl-alpha-rnethoxybenzylphosphine oxide. The product is then recrystallized from acetonitrile.

EXAMPLE II Diphenyl-Alpha-Methoxy-J -Naphthylmethylphosphine Oxide Example I is repeated in every essential respect with the exception that naphthaldehyde is used in lieu of benzaldehyde and the corresponding product, diphenyl-alphamethoxy-l-naphthylrnethylphosphine oxide, is recovered.

EXAMPLE III Di pheny l-A l pha-M ezhoxy-Para-chlorobenzy lphosphi ne Oxide Example I is repeated in every essential respect with the exception that para-chlorobenzaldehyde is used in (lieu of benzaldehyde and the corresponding product, diphenyl-alpha-methoxy-para-chlorobenzylphosphine oxide, is recovered.

I claim: 1. A tertiary alpha-alkoxyphosphine oxide of the formula I? t R2PCR No references cited. 

1. A TERTIARY ALPHA-ALKOXYPHOSPHINE OXIDE OF THE FORMULA 